Mixture of 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone and benzodioxanones and use thereof in augmenting or enhancing the aroma or taste of consumable materials

ABSTRACT

Described are mixtures of 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone having the structure: ##STR1## and benzodioxanones having the generic structure: ##STR2## wherein Z is benzo or cyclohexano and uses thereof in augmenting or enhancing the aroma or taste of consumable materials including foodstuffs and fragrances.

This is a divisional of application Ser. No. 368,640, filed Apr. 15,1982, which, in turn, is a continuation-in-part of application for U.S.Letters Patent, Ser. No. 354,111 filed on Mar. 2, 1982 now abandoned.

Sweet, lactonic, coconut-like, creamy, coumarin-like, waxy,heliotropin-like, fruity, juicy, rum, sugary and woody nuances arehighly desirable in smoking tobacco prior to smoking and sweet,smoothing rich, coumarin-like, creamy, coconut-like, rum-like andcaramellic aroma and taste nuances are highly desirable in smokingtobacco on smoking in the main stream and in the side stream.

Coumarinic organoleptic characteristics have heretofore been provided inconsumable material by coumarin or homologues or analogues thereofhaving the structures: ##STR3##

Coumarin, 1,2-benzopyrone having the structure: ##STR4## is described in"Perfume and Flavor Chemicals (Aroma Chemicals)" by Stephen Arctander,1969 (Monograph 704) as being extensively used in perfumery to supportherbaceous odors, lavender, lavendin, rosemary, citrus oils, oakmoss,etc. and as a fixative in numerous types of fragrances. Arctander statesthat coumarin is almost a standard ingredient in Fougere types with amylsalicylate and lavender notes with or without oakmoss. Arctander statesthat coumarin is not permitted for food use in the United States ofAmerica and is also banned from food flavorings in a number of othercountries. Arctander further states that the hazardous level of coumarinis estimated at three grams per day for adult human beings. Accordingly,it has been found necessary in the flavor and fragrance industry to findone or a mixture of suitable replacements for coumarin. In U.S. Pat. No.4,294,266 and in U.S. Pat. No. 4,241,097 bicyclic compounds definedaccording to the generic structure: ##STR5## wherein Z is benzo orcyclohexano which generic structure includes the structures: ##STR6##were designed as substitutes for 6-methyl coumarin, 7-methyl coumarinand coumarin itself. However, the compounds having the genericstructure: ##STR7## although inexpensive replacements for coumarin, donot have all of the desired coumarin nuances necessary to be a totalreplacer therefor. Accordingly, a need has arisen for a compound ormixture of compounds which can totally replace coumarin yet which isinexpensive and organoleptically compatible with other flavorants oraromatizing agents in consumable materials.

Tetrahydro naphthalene derivatives are known in the prior art foraugmenting or enhancing the aroma or taste of tobaccos. Thus, thecompound defined according to the structure: ##STR8## is disclosed inU.K. Patent Specification No. 1,226,730 and in U.S. Pat. No. 3,217,717as useful for augmenting or enhancing the aroma or taste of smokingtobacco. It is indicated in U.K. Patent Specification No. 1,226,730(published on Mar. 31, 1971) that the compound defined according to thestructure: ##STR9## may be produced by reacting the compound having thestructure: ##STR10## with isopropenyl acetate in order to make a mixtureof compounds defined according to the structure: ##STR11## wherein twoof the non-adjacent dashed lines in the resulting mixture representconjugated carbon-carbon double bonds and the other of the dashed linesrepresent carbon-carbon single bonds; and reacting the resulting mixturedefined according to the structure: ##STR12## with methyl vinyl ketoneaccording to the reaction: ##STR13## wherein in the resulting mixturedefined according to the structure: ##STR14## one of R₃ or R₄ is acetyland the other of R₃ or R₄ is hydrogen and one of R₁ or R₂ is acetoxy andthe other of R₁ or R₂ is methyl; and then rearranging the resultingcompounds defined according to the structure: ##STR15## (with theexception of the compound having the structure: ##STR16## which will notso rearrange), according to the reaction: ##STR17## However, thecompound defined according to the structure: ##STR18## does not have theinteresting and important coumarinic-type properties which provide theneed that is provided by the material of the instant invention definedaccording to the structure: ##STR19## Indeed, the composition of matterof the instant invention, the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone, has properties whichare unexpected and unobvious and advantageous from an organolepticstandpoint.

The prior art has indicated that the compound defined according to thestructure: ##STR20## may be prepared by means of a decarboxylation of"Hagemann's Ester" which has the structure: ##STR21## according to thereaction: ##STR22## Hagemann's Ester is shown in the prior art to beprepared by reacting two moles of acetoacetic ester with one mole offormaldehyde. Indeed, the compound defined according to the structure:##STR23## prepared in this manner is shown to be useful in augmenting orenhancing the aroma or taste of foodstuffs, e.g. non-alcoholicbeverages, ice creams, candy, baked goods, gelatines, pudding, milk anddairy products in Fenaroli's Handbook of Flavor Ingredients, secondedition, volume 2 published by the CRC Press at page 360. Furthermore,Stoll, et al, Helv. Chim. Acta. 30, 2019, 1947 indicates that thecompound having the structure: ##STR24## is a natural constituent ofMenth.pulegium In addition, Fenaroli's Handbook of Flavor Ingredients atpage 400 indicates that the compound having the structure: ##STR25## isuseful in augmenting or enhancing the aroma or taste of foodstuffs.

In preparing the compound defined according to the structure: ##STR26##in order to further prepare the compound having the structure: ##STR27##it has been the practice to discard the higher boiling fractions. It isin these higher boiling fractions that the compound having thestructure: ##STR28## exists. Heretofore, the prior art has failed todisclose and the flavor and fragrance industry has failed to ascertainthat the compound defined according to the structure: ##STR29## has anyutility whatsoever in augmenting or enhancing the aroma or taste ofconsumable materials.

Indeed, heretofore the prior art has disclosed complicated anduneconomical processes for preparing the compound having the structure:##STR30## thusly: Prochazka at Chem. Abstracts volume 42:8162h disclosesthe complicated process: ##STR31##

Wilds and Werth, J. Org. Chem. 17, 1149(1952) applied a Robinsonannelation reaction utilizing a quaterny ammonium derivative to make atricyclic material from a bicyclic material. Applying this type ofreaction, it is possible to form4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone according to thefollowing reaction sequence: ##STR32##

Marshall, et al, Tetrahedron Lett. 1971, (41) 3795-8 disclosed adifficult to perform synthesis of4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone by means of a Birchreduction using liquid ammonia.

Hexahydro naphthalenones are known in nature and are known flavorants innature as is stated in the publication Tob. Sci. 1972 16, 107-112(abstracted at Chem. Abstracts Volume 78, 2099y) wherein the compoundhaving the structure: ##STR33## is shown to be present in tobaccoflavor. The compound having the structure: ##STR34## has organolepticproperties different in kind and unexpectedly and unobviously differentfrom the organoleptic properties of the compound having the structure:##STR35##

Also, the compound of U.K. Patent Specification No. 1,226,730 having thestructure: ##STR36## has sweet, woody, herbaceous, fruity notes in themain stream and the side stream on smoking in a smoking tobaccocomposition. It enhances tobacco character and imparts Virginia-likenotes.

From a flavor standpoint, the compound having the structure: ##STR37##has a dogwood, oak-like, Virginia tobacco-like aroma and tastecharacteristic at 0.2 ppm. From a perfumery standpoint, the compoundhaving the structure: ##STR38## has a powerful tobacco, hay, dried fruitodor and is useful in clover fragrances. However, the compound havingthe structure: ##STR39## does not have the organoleptic utilities of thecompound having the structure: ##STR40## as will be seen from theinstant specification.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the crude reaction product of Example Iresulting from the reaction of isopropenyl acetate with the compoundhaving the structure: ##STR41## in order to form a mixture of compoundsdefined according to the structures: ##STR42## which mixture representsthe compounds defined according to the structures: ##STR43##

FIG. 2 is the GLC profile for bulked fractions 8-13 of the distillationproduct of the reaction product of Example II containing the compoundshaving the structures: ##STR44##

FIG. 3 is the NMR spectrum for the acetate of5-methyl-7-acetyl-bicyclo[2.2.2]oct-5-en-1-ol produced according toExample II having the structure: ##STR45## (CFCl₃ solvent; FieldStrength 100 MHz).

FIG. 4 is the GLC profile for the crude reaction product for Example IIIcontaining the compound having the structure: ##STR46##

FIG. 5 is the mass spectrum for the compound having the structure:##STR47## of Example III.

FIG. 6 is the NMR spectrum for the crystalline compound producedaccording to Example III having the structure: ##STR48## (CFCl₃ solvent;Field Strength 100 MHz).

FIG. 7 is the infra-red spectrum for the crystalline compound having thestructure: ##STR49## produced according to Example III.

FIG. 8 is the GLC profile for the crude reaction product producedaccording to Example V containing the compound having the structure:##STR50## as well as the compound,4,4A,5,6-tetrahydro-7-methyl-2-(3H)naphthalenene having the structure:##STR51##

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the crude reaction product of Example Icontaining compounds defined according to the structures: ##STR52## Thepeak indicated by the reference numeral "1" is the peak for the startingmaterial for the reaction having the structure: ##STR53## The peakindicated by the reference numeral "2" is a complex peak containing amixture of the compounds defined according to the structures: ##STR54##

FIG. 8 is the GLC profile for the crude reaction product for productionof the compound having the structure: ##STR55## (conditions: 2'×1/8"Carbowax column programmed at 100°-220° C. at 8° C. per minute). Thepeak indicated by reference numeral "3" is the peak for the solvent forthis reaction. The peak indicated by reference numeral "4" is the peakfor the reaction product having the structure: ##STR56##

The peak indicated by reference numeral "5" is the peak for the compoundhaving the structure: ##STR57##

THE INVENTION

It has now been discovered that novel solid and liquid foodstuff,chewing gum, toothpaste, medicinal product, chewing tobacco compositionsand flavoring compositions therefor having coumarin-like, coconut,lactonic, hay-like, macaroon-like and sweet aromas and hay-like,coumarin-like, coconut-like, lactonic, almond-like, macaroon-like, sweetand bitter tastes; and novel perfume compositions, perfumed articles(such as solid or liquid anionic, cationic, nonionic or zwitterionicdetergents, fabric softener compositions, disposable fabric softenerarticles, cosmetic powders and perfumed polymers) and colognes havingnatural and diffusive coumarin-like, tonka-like, fruity, tobacco-likeand sweet rum aroma profiles with spicy, hay and tobacco-like topnotes;as well as novel smoking tobaccos and smoking tobacco flavoringcompositions having, prior to smoking, sweet, lactonic, coconut-like,coumarin-like, creamy, waxy, heliotropine-like, fruity, juicy, rum,sugary and woody aroma nuances and on smoking in both the main streamand the side stream sweet, smoothing rich, coumarin-like, creamy,coconut-like, rum-like and caramellic aroma and taste nuances may beprovided by the utilization of4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone having the structure:##STR58## having a purity of 85% or greater. The4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone in the crystallinestate of about 100% purity having the structure: ##STR59## is a novelcomposition of matter.

The 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our inventionhaving the structure: ##STR60## may be produced according to twoalternative and novel processes. The first process involves the reactionof two moles of formaldehyde with three moles of acetoacetic esteraccording to a reaction which may proceed in one of the followingpostulated fashions: ##STR61## After formation of the polycarboxylicacid ketoester, the diester is then saponified, acidified and finallyheated whereby the carboxylic acid moieties are removed bydecarboxylation with the evolution of carbon dioxide in order to formthe 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone having thestructure: ##STR62## In this reaction, the mole ratio of acetoaceticester:formaldehyde is 3:2. The length of time required for the reactionto proceed must be such that the additional formaldehyde and acetoaceticester react with the preformed acetoacetic ester-formaldehyde adduct(probably the "Hagemann's ester"). The reaction to form thepolycarboxylate preferably takes place in the presence of a base such aspiperadine. The formaldehyde may be formaldehyde itself or aformaldehyde source such as paraformaldehyde or formalin (40% aqueousformaldehyde). The reaction temperature varies between 95° C. and 110°C. and the reaction time varies between one hour and four hours.Reaction time of less than one hour and reaction temperatures of lessthan 95° C. will not give rise to economical yields of thepolycarboxylic acid ester intermediate but instead give rise to highyields of the undesired Hagemann's ester. At the completion of theformation of the polycarboxylic acid ester, the reaction product isdecarboxylated using a decarboxylation procedure which is theacidification of the reaction mass using such concentrated protonic acidas concentrated sulfuric acid, para toluenesulfonic acid or mixtures ofsame. The decarboxylation time is preferably about five hours and thedecarboxylation temperature is preferably between 85° C. and 105° C. atpressures of about atmospheric pressure. The equivalent ratio ofpolycarboxylic acid ester:protonic acid should be about 1:1. If anyreagent is used in excess, it is the protonic acid. Thus, for example,when using sulfuric acid as a decarboxylation reagent, the weight ratioof sulfuric acid (concentrated): polycarboxylic acid ester variesbetweeen about 3:4 up to about 4:3.

At the end of the reaction, the reaction product is fractionallydistilled and the fraction distilling at a vapor temperature of 96° C.and a liquid temperature of 156° C.; and a vacuum of 3 mm/Hg pressure isapproximately 85-90% 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenonehaving the structure: ##STR63##

The compound having the structure: ##STR64## may also be economicallyprepared by decarboxylating the Hagemann's ester formed from thereaction of one mole of formaldehyde and two moles of acetoacetic esterwhereby the compound having the structure: ##STR65## is formed. Thiscompound is then reacted with isopropenyl acetate to form a mixture ofcompounds defined according to the structure: ##STR66## wherein two ofthe dashed lines not adjacent to one another represent conjugatedcarbon-carbon double bonds and the other of the dashed lines representcarbon-carbon single bonds. The compounds have the structures: ##STR67##This mixture is then conveniently reacted via a Diels-Alder reaction athigher temperatures or using a Lewis acid catalyst such as stannicchloride or zinc chloride or boron-trifluoride etherate with methylvinyl ketone having the structure: ##STR68## thereby forming a mixtureof compounds defined according to the structure: ##STR69## wherein inthe mixture, one of R₃ or R₄ is hydrogen and the other of R₃ or R₄ isacetyl and one of R₁ or R₂ is methyl and the other of R₁ or R₂ isacetoxy, to wit compounds having the structures: ##STR70## It has beenpostulated that the compound having the structure: ##STR71## can berearranged by heating with base or solutions of base to form thecompound having the structure: ##STR72## However, the reaction may bebest shown as a rearrangement thusly: ##STR73## In general, the sequenceof reactions described above is as follows: ##STR74##

The reaction of the ketone having the structure: ##STR75## with theisopropenyl acetate having the structure: ##STR76## to form the mixtureof compounds defined according to the structure: ##STR77## preferablytakes place in the presence of a protonic acid catalyst such asparatoluene sulfonic acid, sulfuric acid or phosphoric acid. The moleratio of 3-methyl-cyclohexenone: isopropenyl acetate may vary from about0.5:1 up to about 1.5:1 with a preferred mole ratio of 1:1. Theconcentration of protonic acid in the reaction mass may vary from about0.01% up to about 0.5%. The reaction temperature may vary from about100° C. up to about 150° C. at from atmospheric pressure up to about 5atmospheres. During the reaction, the water of reaction is continuouslyremoved. At the end of the reaction, the reaction product is distilledyielding the mixture of compounds defined according to the structure:##STR78## The resulting mixture is further reacted with methyl vinylketone according to the reaction: ##STR79## This reaction, a Diels-Alderreaction, may take place without a catalyst (e.g. a Lewis acid catalyst)at higher temperatures, e.g. reflux temperatures, e.g. from 110° up to150° C. at pressures of atmospheric up to about 5 atmospheres or thereaction may take place at lower temperatures, e.g. 70° C. using a Lewisacid catalyst such as stannic chloride, borontrifluoride etherate orzinc chloride. When using no catalyst at higher temperatures, theDiels-Alder reaction takes place preferably at reflux conditions over aperiod of between four hours and eight hours. At the end of thereaction, the resulting reaction mixture is distilled yielding a mixtureof compounds defined according to the structures: ##STR80##

The resulting mixture of compounds is then subjected to a rearrangementreaction shown mostly: ##STR81## which takes place in the presence of astrong base such as sodium hydroxide, potassium hydroxide or lithiumhydroxide. The rearrangement reaction is carried out in the presence ofan inert solvent such as methanol, isopropanol or ethanol which solventwill permit conventional refluxing at a temperature such that the timeof reaction will vary between about one hour and about three hours. Toolow a boiling solvent will necessitate a pressure substantially higherthan atmospheric pressure thereby giving rise to the requirement of moreexpensive complicated apparatus or such a long time of reaction as torender the cost of carrying out the reaction prohibitively high.

At the end of the reaction, the reaction product is distilled and ifdesired, the distillation fractions containing 99% or more of4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone having the structure:##STR82## are crystallized thereby yielding a highly pure form of4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone which form is novel.

The compound of our invention;4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone, having the structure:##STR83## is capable of supplying and/or potentiating certain flavor andaroma notes usually lacking in many fruit flavors as well as tobaccoflavors heretofore. Furthermore, the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our invention iscapable of supplying certain fragrance notes usually lacking in manyperfumery materials, for example, Fougere formulations, lavendinformulations, citrusy formulations and oakmoss-type formulations. Inaddition, this material is capable of acting as a fixative in perfumerywhile augmenting or enhancing certain aroma nuances in itself.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs includes soups, convenience foods, beverages,dairy products, candies, vegetable cereals, soft drinks, snacks and thelike.

As used herein, the term "medicinal products" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, cough drops and chewable medicinal tablets.

The term "chewing gum" is intended herein to be a foodstuff compositioncomprising a substantially water-insoluble, chewable plastic gum basesuch as chicle, or substitutes therefor, including jelutong, guttakay,rubber or certain comestible natural or synthetic resins or waxes.Incorporated with the gum base in admixture therewith may beplasticizers or softening agents, e.g. glycerine and a flavoringcomposition which incorporates one or more of the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenones of our invention,and, in addition, sweetening agents which may be sugars, includingsucrose or dextrose and/or artificial sweeteners such as cyclamates orsaccharin. Other optional ingredients may be present.

The term "augment" in its various forms is used herein to mean thesupplying, modifying or imparting of a flavor or aroma characteristicnote or nuance to an otherwise bland, relatively tasteless ornon-odorous substance or modifying an existing flavor or aromacharacteristic where the natural flavor is deficient in some regard, orsupplementing the existing flavor or aroma impression to modify itsquality, character, taste or aroma.

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note or nuance.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is required that any suchmaterial be "ingestibly acceptable" and thus non-toxic or otherwisenon-deleterious, particularly from an organoleptic standpoint wherebythe ultimate flavor and/or aroma of the consumable material used doesnot cause the consumable material to have unacceptable aroma and tastenuances.

It is a further requirement that such material be organolepticallycompatible with the foodstuff with which it is used so that the flavorand aroma nuances of such material, taken together with the flavor andaroma nuances of the foodstuff (as a whole) give rise to a harmoniouslyaesthetically pleasing aroma and taste profile. Such material, ingeneral, may be characterized as flavoring adjuvants or vehiclescomprising broadly, stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g. sodium chloride;antioxidants, e.g. calcium and sodium ascorbate, ascorbic acid,butylated hydroxyanisole (mixture of 2- and3-tertiary-butyl-4-hydroxyanisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like andsequestrants, e.g. citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g. agar agar,carrageenan, cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth, gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectins and emulsifiers, e.g. mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g. sucrose, corn syrup and the like.

Surface active agents include emulsifying agents, e.g. fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g. benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like,starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g. sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like,colorants, e.g. carminic acid, cochineal, tumeric and curcumin and thelike, firming agents such as aluminum sodium sulfate, calcium chlorideand calcium glyconate, texturizers, anti-caking agents, e.g. aluminumcalcium sulfate and tribasic calcium phosphate, enzymes, yeast foods,e.g. calcium lactate and calcium sulfate, nutrient supplements, e.g.iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid, and 2-methyl-cis-3-pentenoic acid; ketonesand aldehydes, e.g. acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl,beta,beta-dimethyl-acrolein, n-hexanal, 2-hexanal, cis-3-hexenal,2-heptenal, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,2-methyl-3-butanone, 2-pentanone, 2-pentenal and propanal; alcohols suchas 1-butanol, benzyl alcohol, 1-borneol, trans-2-buten-1-ol, ethanol,geraniol, 1-hexanol, 2-heptanol, trans-2-hexenol-1,cis-3-hexen-1-ol,3-methyl-3-buten-1-ol, 1-pentenol, 1-penten-3-ol,p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol,phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate, esters, suchas butyl acetate, ethyl acetate, ethyl acetoacetate; ethyl benzoate,ethyl butyrate, ethyl caproate, ethyl cinnamate, ethyl crotonate, ethylformate, ethyl isobutyrate, ethyl isovalerate, ethylalpha-methyl-butyrate, ethyl propionate, ethyl salicylate,trans-2-hexenyl acetate, hexyl acetate, 2-hexenyl butyrate, hexylbutyrate, isoamyl acetate, isopropyl butyrate, methyl acetate, methylbutyrate, methyl caproate, methyl isobutyrate, methyl-2-methyl-butyrate,propyl acetate, amyl acetate, amyl butyrate, benzyl salicylate, dimethylanthranilate, ethyl methylphenyl-glycidate ethyl succinate isobutylcinnamate and terpenyl acetate; essential oils such as jasmin absolute,rose absolute, orris absolute, lemon essential oil, Bulgarian rose, yarayara, natural raspberry oil and vanilla; lactones, sulfides, e.g. methylsulfide and other materials such as maltol, acetoin and acetals (e.g.1,1-diethoxyethane,1,1-dimethoxyethane and dimethoxymethane.

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e. foodstuff, whether simulated or natural, and should, in any event,be capable of providing an environment in which the cyclic chemicalcompounds can be dispersed or admixed to provide a homogeneous medium.In addition, selection of one or more flavoring adjuvants, as well asthe quantities thereof will depend upon the precise organolepticcharacter desired in the finished product. Thus, in the case offlavoring compositions, ingredient selection will vary in accordancewith the foodstuff to which the flavor and aroma are to be imparted. Incontradistinction, in the preparation of solid products, e.g. simulatedfoodstuffs, ingredients capable of providing normally solid compositionsshould be selected such as various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount of4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone employed in aparticular instance can vary over a relatively wide range whereby itsdesired organoleptic effects (having reference to the nature of theproduct) are achieved. Thus, correspondingly greater amounts would benecessary in those instances wherein the ultimate food composition to beflavored is relatively bland to the taste, whereas relatively minorquantities may suffice for purposes of enhancing the composition merelydeficient in natural flavor or aroma. The primary requirement is thatthe amount selected (to be effective) be sufficient to augment orenhance the organoleptic characteristics of the parent composition(whether foodstuff per se or flavoring composition).

The use of insufficient quantities of4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone will, of course,substantially vitiate any possibility of obtaining the desired resultswhile excess quantities prove needlessly costly and in extreme cases,may disrupt the flavor-aroma balance, thus proving self-defeating.Accordingly, the terminology "effective amount" and "sufficient amount"is to be accorded a significance in the context of the present inventionconsistent with the obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, it is found thatquantities of 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone rangingfrom a small but effective amount, e.g. 0.1 parts per million up toabout 20 parts per million by weight based on total composition aresuitable. Concentrations in excess of the maximum quantity stated arenot normally recommended, since they fail to provide commensurateenhancement of organoleptic properties. In those instances, wherein the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone is added to thefoodstuff as an integral component of a flavoring composition, it is, ofcourse, essential that the total quantity of flavoring compositionemployed by sufficient to yield an effective4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone concentration in thefoodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone in concentrationsranging from about 0.1% up to about 15% by weight based on the totalweight of said flavoring composition.

The compositions described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our invention with,for example, gum arabic, gum tragacanth, carrageenan and the like, andthereafter spray-drying the resultant mixture whereby to obtain theparticulate solid product. Pre-prepared flavor mixes in powder form,e.g. a fruit flavored powdered mix, are obtained by mixing the driedsolid components, e.g. starch, sugar and the like and4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone in a dry blender untilthe requisite degree of uniformity is achieved.

It is presently preferred to combine with the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone the followingadjuvants:

p-Hydroxybenzyl acetone;

Geraniol;

Acetaldehyde;

Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Vanillin;

Methyl cinnamate;

Ethyl pelargonate;

Methyl anthranilate;

Isoamyl acetate;

Isobutyl acetate;

Alpha ionone;

Ethyl butyrate;

Acetic acid;

Gamma-undecalactone;

1-(3-(methylthio)butyryl-2,6,6-trimethyl cyclohexene;

1(3(methylthio)butyryl)-2,6,6-trimethyl-1,3-cyclohexadiene;

Naphthyl ethyl ether;

Diacetyl;

Ethyl acetate;

Anethole;

Isoamyl butyrate;

Cis-3-hexenol-1;

2-Methyl-2-pentenoic acid;

2-Methyl-cis-3-pentenoic acid;

Ethyl-2-methyl-cis-3-pentenoate;

Methyl-2-methyl-cis-3-pentenoate;

Elemecine (4-allyl-1,2,6-trimethoxy benzene);

Isoelemacine (4-propenyl-1,2,6-trimethoxy benzene); and

2-(4-hydroxy-4-methylpentyl)norbornadiene prepared according to U.S.Pat. No. 3,886,289, issued on May 27, 1975.

An additional aspect of our invention provides an organolepticallyimproved smoking tobacco product and additives therefor as well asmethods of making the same which overcome specific problems heretoforeencountered in which specific desired sweet, creamy, coumarin-like,smoothing rich, fruity, rum, sugary and woody flavor and aromacharacteristics are created or enhanced and may be readily controlledand maintained at the desired uniform level regardless of variations inthe tobacco components of the blend.

This invention further provides improved tobacco aditives and methodswhereby various desirable sweet; lactonic, coconut-like, creamy,coumarin-like, waxy, heliotropin-like, fruity, juicy, rum-like, sugaryand woody aroma characteristics may be imparted to smoking tobaccoproducts prior to smoking and sweet, smoothing rich, coumarin-like,creamy, coconut-like, rum-like and caramellic aroma and tastecharacteristics may be readily imparted to smoking tobacco products onsmoking in the main stream and in the side stream and may be readilyvaried and controlled to produce the desired uniform flavoring and aromacharacteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substitute therefor (e.g. dried lettuce leaves)an aroma and flavor additive containing as an active ingredient4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone having the structure:##STR84##

In addition to the 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone ofour invention, other flavoring and aroma additives may be added to thesmoking tobacco material or substitute therefor either separately or inadmixture with the 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone ofour invention as follows:

I. Synthetic Materials

Beta-ethyl-cinnamaldehyde;

Eugenol;

Dipentene;

β-Damascone;

β-Damascenone;

Maltol;

Ethyl maltol;

Delta undecalactone;

Delta decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2,6-Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropyl acetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)-decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethyl naphtho-(2,1,-b-)-furan;

4-Hydroxy hexanoic acid, gamma lactone;

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372, issued on June 29, 1971.

II. Natural Oils

Celery seed oil;

Coffee extract;

Bergamot Oil;

Cocoa extract;

Nutmeg oil; and

Origanum oil;

An aroma and flavoring concentrate containing the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our invention andif desired, one or more of the above indicated additional flavoringadditives may be added to the smoking tobacco material, to the filter orto the leaf or paper wrapper. The smoking tobacco material may beshredded, cured, cased and blended tobacco material or reconstitutedtobacco material or tobacco substitutes (e.g. lettuce leaves) ormixtures thereof. The proportions of flavoring additives may be variedin accordance with taste but insofar as the augmentation or theenhancement or the imparting of the sweet, lactonic, coconut-like,creamy, coumarin-like, waxy, heliotropin-like, fruity, juicy, rum,sugary and woody aroma notes are concerned and insofar as the sweet,smoothing rich, coumarin-like, creamy, coconut-like, rum-like andcaramellic aroma notes on smoking are concerned, we have found thatsatisfactory results are obtained if the proportion by weight of the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone to smoking tobaccomaterial is between 100 ppm and 1,500 ppm (0.025%-0.15%) of the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone to the smoking tobaccomaterial. We have found further that satisfactory results are obtainedif the proportion by weight of the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone used to flavoringmaterial is between 1,000 and 10,000 ppm (0.1-1.0%).

Any convenient method for incorporating the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our invention maybe employed. Thus the 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenonetaken alone or along with other flavoring additives may be dissolved ina suitable solvent such as ethanol, n-pentane, diethyl ether and/orother volatile organic solvents and the resulting solution may either bysprayed on the cured, cased and blended tobacco material or the tobaccomaterial may be dipped into such solution. Under certain circumstances,a solution of 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone takenalone or further together with other flavoring additives as set forthabove, may be applied by means of a suitable applicator such as a brushor roller on the paper or leaf wrapper for the smoking product or it maybe applied to the filter by either spraying, dipping or coating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases the tobacco treated may have the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone in excess of theamounts or concentrations above indicated, so that when blended withother tobaccos, the final product will have the percentage within theindicated range.

In accordance with one specific example of our invention, an aged, curedand shredded domestic burley tobacco is spread with a 20% ethyl alcoholsolution of 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone to providea tobacco composition containing 800 ppm by weight of4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone on a dry basis.Thereafter the alcohol is removed by evaporation and the tobacco ismanufactured into cigarettes by the usual techniques. The cigarette,when treated as indicated, has a desired and pleasing aroma which isdetectable in the main and side streams when the cigarette is smoked.This aroma is described as being sweet, smoothing rich, coumarin-like,creamy, coconut-like, rum-like and caramellic.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco,other tobacco products formed from sheeted tobacco dust or fines mayalso be used. Likewise the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our invention canbe incorporated with material such as filter tip materials, seam paste,packaging materials and the like which are used along with tobacco toform a product adapted for smoking. Furthermore, the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our invention canbe added to certain tobacco substitutes of natural or synthetic origin(e.g. dried lettuce leaves) and, accordingly, by the term "tobacco" asused throughout this specification, is meant any composition intendedfor human consumption by smoking or otherwise, whether composed oftobacco plant parts or substitute materials or both.

The 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone having thestructure: ##STR85## of our invention either in 85% form (as producedaccording to Example IV infra) or in 100% crystalline form (as producedaccording to Example III infra) or any range there between and one ormore auxilliary perfume ingredients including, for example, alcohols,aldehydes, nitriles, esters, ketones other than the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our invention,cyclic esters, synthetic essential oils, ethers and natural essentialoils may be admixed so that the combined odor of the individualcomponents produces a pleasant and desired fragrance particularly andpreferably insofar as floral fragrances are concerned.

Such perfume compositions usually contain (a) the main note or the"bouquet" or foundation stone of the composition; (b) modifiers whichround off and accompany the main note; (c) fixatives which includeodorous substances which lend a particular note to the perfumethroughout all stages of evaporation and substances which retardevaporation and (d) topnotes which are usually low-boilding,fresh-smelling materials.

In perfume compositions, it is the individual components whichcontribute particular olfactory characteristics but the overall effectof the perfume composition will be the sum of the effects of each of theingredients. Thus, the 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenoneof our invention having the structure: ##STR86## can be used to alterthe aroma characteristics of a perfume composition, for example, byutilizing or moderating the olfactory reaction contributed by anotheringredient in the composition.

The amount of 4,4,A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of ourinvention which will be effective in perfume compositions depends onmany factors, including the other ingredients, their amounts and theeffects which are desired. It has been found that perfume compositionscontaining as little as 0.05% of the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone and even less (e.g.0.02%) can be used to impart natural and diffusive coumarin-like,tonka-like, fruity, tobacco-like, sweet and sweet rum aroma nuances withspicy, hay and tobacco-like topnotes to soaps, cosmetics or otherproducts. The amount employed can range up to 10% of the fragrancecomponents and will depend on considerations of cost, nature of the endproduct, the effect desired on the finished product and the particularfragrance sought.

The 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our inventionis useful taken alone or in perfume compositions as an olfactorycomponent in detergents and soaps, space odorants and deodorants,perfumes per se, colognes per se, toilet water, bath preparations suchas bath oils and bath solids; hair preparations such as lacquers,brilliantines, pomades and shampoos; cosmetic preparations such ascreams, deodorants, hand lotions and sun screens; powders such as talc,dusting powders, face powders and the like. When used as an olfactorycomponent, as little as 0.01% of the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our invention willsuffice to impart a natural and diffusive coumarin-like, tonka-like,fruity, tobacco-like, and sweet rum aroma profile to perfumed articles.Generally no more than 3% of the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our invention basedon the ultimate end product is required in the perfumed article.

Thus insofar as perfumed articles are concerned, the amount of4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our inventionhaving the structure: ##STR87## can vary from 0.01% by weight up to 3.0%by weight based on the total weight of the perfumed article, that is,based on the total weight of such materials as anionic, cationic,nonionic or zwitterionic solid or liquid detergent bases; or fabricsoftener compositions, or fabric softener articles, or perfumedpolymers.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle or carrier for the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our invention. Thevehicle can be a liquid such as a non-toxic alcohol, a non-toxic glycolor the like. The carrier can be an absorbent solid such as a gum (e.g.gum arabic, gum tragacanth, guar gum or xanthan gum) or components forencapsulating the composition (such as gelatin as by coacervation or aurea-formaldehyde prepolymer as by polymerization of a shell around aliquid center).

The 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our inventioncan be also combined in proportions of from 0.1% up to 99.9% of4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone with respect to thebenzodioxanones of United States Letters Patent 4,294,266 issued on Oct.13, 1981, the specification of which is incorporated herein byreference. Thus, the instant invention not only contemplates theorganoleptic utilities of the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone per se having thestructure: ##STR88## but also involves admixtures of4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone having the structure:##STR89## with the bicyclic compounds having the generic structure:##STR90## wherein Z is benzo or cyclohexano.

It will thus be apparent that the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our invention takenalone or further together with the cyclic chemical compounds definedaccording to the structure: ##STR91## wherein Z is benzo or cyclohexanocan be utilized to alter the sensory properties of consumable materialsparticularly organoleptic properties such as flavors and/or fragrancesof a wide variety of consumable materials.

The following examples are illustrative and the invention is to beconsidered to be restricted thereto only as indicated in the appendedclaims. These examples serve to illustrate the processes for producingthe 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone useful in ourinvention and processes for using the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our invention forits organoleptic properties.

All parts and percentages given are by weight unless otherwisespecified.

EXAMPLE I PREPARATION OF ACETOXY CYCLOHEXADIENE DERIVATIVE MIXTURE

Reaction: ##STR92## (wherein in the resulting product, in each of themolecules of the mixture, two of the dashed lines not adjacent to oneanother represent conjugated carbon-carbon double bonds and the other ofthe dashed lines represent carbon-carbon single bonds).

A twelve liter reaction flask (equipped with a 12" stone packed columnand thermometer) is charged with 3,780 grams of 3-methyl-2-cyclohexenonehaving the structure: ##STR93## 4,000 grams of isopropenyl acetatehaving the structure: ##STR94## and 10 grams of para toluenesulfonicacid.

With stirring, the reaction mass is heated to reflux. Acetone (formed inthe reaction) is distilled out between 40°-70° C. (vapor temperature).Completion of the reaction is monitored using GLC. 50 grams of sodiumacetate is added and the product is distilled under vacuum. 5,042 gramsof product is obtained having the following distillation profile:

    ______________________________________                                        Vapor    Liquid                Weight                                         Temp.    Temp.    Pressure     of Fraction                                    (°C.)                                                                           (°C.)                                                                           mm/Hg.       (grams)                                        ______________________________________                                        58       89       12           100                                            58-69     89-150  4            5042 (product)                                 69-102   150-215  5            100                                            ______________________________________                                    

GLC, NMR and IR and mass spectral analyses yield the information thatthe product boiling at 58°-69° C. at 4 mm/Hg pressure consists of thecompounds having the structures: ##STR95##

Fractions 1-10 are bulked for subsequent reaction in Example II.

FIG. 1 is the GLC profile for the crude reaction product prior todistillation (conditions: SF-96 column programmed at 100°-220° C. at 8°C. per minute). The peak indicated by the reference numeral "1" is thepeak for the starting material defined according to the structure:##STR96## The peak indicated by reference numeral "2" is a complex peakcontaining a mixture of compounds defined according to the structure:##STR97## wherein in each of the molecules of the mixture, two of thedashed lines not adjacent to one another represent conjugatedcarbon-carbon double bonds and the other of the dashed lines representcarbon-carbon single bonds.

EXAMPLE II PREPARATION OF METHYL-ACETYL-BICYCLO-[2.2.2]OCT-5-ENOLACETATE INCLUDING 5-METHYL-7-ACETYL BICYCLO-[2.2.1]OCT-5-EN-1-OL ACETATE

Reaction: ##STR98## (wherein in the starting reactant mixture, in eachof the molecules, two of the dashed lines not adjacent to one anotherrepresent conjugated carbon-carbon double bonds and the other of thedashed lines represent carbon-carbon single bonds; and in the reactionproduct mixture represented by the structure: ##STR99## one of R₃ or R₄represents hydrogen and the other of R₃ or R₄ represents acetyl and oneof R₁ or R₂ represents methyl and the other of R₁ or R₂ representsacetoxy).

A 12 liter reaction flask (equipped with stirrer, condenser, additionfunnel and thermometer) is charged with 6,243 grams of the enol estermixture produced according to Example I defined by the structure:##STR100## 3,215 grams of methyl vinyl ketone and 10 grams ofhydroquinone. The resulting mixture is heated to reflux slowly. As thereaction proceeds to completion, the pot temperature rises from 90°-170°C. Completion of the reaction is monitored using GLC. After no moreproduct is formed, the reaction mixture is transferred to a distillationflask and distilled. 3,155 grams of the product mixture is obtainedhaving the following distillation profile:

    ______________________________________                                        Vapor   Liquid              Weight of                                         Temp.   Temp.    Pressure   Fraction                                          (°C.)                                                                          (°C.)                                                                           mm/Hg.     (grams)                                           ______________________________________                                        88-92   131-150  25-5       1,324 (recovered starting                                                     material)                                         122-118 151-232  5          3,155 (product)                                   ______________________________________                                    

The 3,155 grams of product will be utilized in the process of ExampleIII. The 3,155 grams of product, boiling at 118°-122° C. at 5 mm/Hgpressure contains compounds defined according to the structures:##STR101## as confirmed by NMR, IR and mass spectral analyses.

FIG. 2 is the GLC profile for bulked fractions 8-13 of the foregoingdistillation product.

FIG. 3 is the NMR spectrum for the compound5-methyl-7-acetyl-bicyclo[2.2.2]oct-5-en-1-ol acetate produced accordingto this example, having the structure: ##STR102## (CFCl₃ solvent; FieldStrength 100 MHz).

EXAMPLE III PREPARATION OF CRYSTALLINE4,4A,5,6-TETRAHYDRO-7-METHYL-2-(3H)-NAPHTHALENONE

Reaction: ##STR103## (wherein in the starting material, one of R₃ or R₄is hydrogen and the other of R₃ or R₄ is acetyl; and one of R₁ or R₂ ismethyl and the other of R₁ or R₂ is acetoxy).

A 12 liter reaction flask (equipped with stirrer, thermometer, additionfunnel and large condenser) is charged with 200 grams of sodiumhydroxide pellets and 6 liters of methanol. The mixture is stirred untilthe pellets dissolve and the mass is heated to reflux. To the refluxingsolution, 650 grams of the bicyclic adduct defined according to thestructures: ##STR104## produced according to Example II is added slowlyto the reaction mass. The reaction mass is refluxed for a period of 12hours and then cooled. The reaction mass is decomposed by adding it to 6liters of ice water and extracted with diethyl ether; washed with asaturated sodium chloride solution and dried. The solvent is strippedatmospherically and the product is distilled under vacuum at 138° C. at2 mm/Hg pressure yielding 350 grams of crude product.

This material (the crude mixture) contains impurities. Pure (99%+)material is obtained by using column chromatography. Thus, speciallytreated silica gel is used as a solid support. Cyclohexane is used as asolvent. Various cuts are taken and analyzed using GLC analysis. Thefractions containing 99%+ product, that is the product having thestructure: ##STR105## are concentrated and the product concentrate istreated with copper powder to remove the sulfur aroma. Thus, theconcentrated product is admixed in hot methanol with copper powder. Theresulting mixture is stirred for a period of 3 hours. The copper powderis filtered from the solution and the solution is then admixed withcharcoal. The charcoal is separated from the mixture by filtration andthe resultant 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone havingthe structure: ##STR106## (purity greater than 99%) is precipitated fromthe methanol solution (by means of slow crystallization). This materialhas a melting point of 31°-33° C.

FIG. 4 is the GLC profile for the crude reaction product of this example(isothermal at 220° C.).

FIG. 5 is the mass spectrum for the crystals of4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone having the structure:##STR107## produced according to this example.

FIG. 6 is the NMR spectrum for the crystalline4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone having the structure:##STR108## produced according to this example (CFCl₃ solvent; FieldStrength, 100 MHz).

FIG. 7 is the infra-red spectrum for the crystalline4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone having the structure:##STR109## produced according to this example.

EXAMPLE IV PREPARATION OF4,4A,5,6-TETRAHYDRO-7-METHYL-2-(3H)-NAPHTHALENONE BY REACTING THREEMOLES OF ACETOACETIC ESTER WITH TWO MOLES OF FORMALDEHYDE FOLLOWED BYDECARBOXYLATION

Postulated possible reaction sequences: ##STR110##

Into a 22-liter Morton reaction flask equipped with heating mantle, airstirrer, thermometer, addition funnel and reflux condenser, 3,900 gramsof ethyl acetoacetate and 450 grams of paraformaldehyde are added withstirring. The resulting mixture is maintained at 23° C. and whilemaintaining the mixture at 23° C., over a 20 minute period, 150 ml ofpiperidine is added with stirring to the reaction mass.

The reaction mass is then heated to 105° C. with stirring and maintainedat 95°-105° C. for a period of 1.5 hours. At the end of the 1.5 hours,the reaction mass is cooled to room temperature and 2,960 grams of 92%sulfuric acid in 9 liters of water is added to the reaction mass. Thereaction mass is then refluxed at 90° C. for a period of 4 hours withstirring. At the end of the 4 hour "decarboxylation" period, thereaction mass is cooled to room temperature using an ice bath andtransferred to a 50 liter separatory funnel. The reaction mass isextracted with three 2 liter portions of methylene dichloride. Theorganic layers are combined and washed with one 4 liter portion of waterfollowed by one 2 liter portion of saturated sodium bicarbonate. Theresulting liquid is then dried over anhydrous sodium sulfate, filteredand stripped of methylene dichloride at 80° C. at atmospheric pressure.

The reaction mass is then distilled yielding the following fractions ona 1' Goodloe column:

    ______________________________________                                                  Vapor   Liquid                                                      Fraction  Temp.   Temp.      Pressure                                                                             Reflux                                    Number    (°C.)                                                                          (°C.)                                                                             mm/Hg. Ratio                                     ______________________________________                                        1         40/51   120/127    3/3    9:1                                       2         64      129        3      9:1                                       3         96      135        3      9:1                                       4         96      141        3      9:1                                       5         108     149        3      4:1                                       6         110     147        3      4:1                                       7         108     150        3      4:1                                       8         96      156        3      4:1                                       ______________________________________                                    

Fractions 1-7 are bulked and are analyzed to be less than 80% of thecompound having the structure: ##STR111## and more than 20% of thecompound having the structure: ##STR112##

Fraction 8 is a composition of matter containing 86% of the compoundhaving the structure: ##STR113## and this fraction is set aside forsubsequent organoleptic utilization.

EXAMPLE V PREPARATION OF METHYL CYCLOHEXENONE FROM TWO MOLES OFACETOACETIC ESTER AND ONE MOLE OF FORMALDEHYDE FOLLOWED BYDECARBOXYLATION ##STR114##

Into a 22 liter reaction flask equipped with heating mantle, airstirrer, reflux condenser, addition funnel and thermometer is placed2,600 grams of ethyl acetoacetate and 300 grams of paraformaldehyde.Over a period of 8 minutes, 100 ml piperidine is added to the reactionmass while maintaining the temperature at 25°-26° C. The reaction massis then heated to 90°-93° C. (reflux) and maintained at that temperaturefor a period of 1.25 hours. At the end of that period of time, thereaction mass is cooled and 2,960 grams of 93% sulfuric acid in 9 litersof water is added. The reaction mass is then heated to 97°-99° C.(refluxing) and maintained at that temperature for a period of 17 hourswith stirring and refluxing. The reaction mass is then cooled to roomtemperature and steam distilled over a period of 9 hours at 94°-95° C.

The steam distillate is transferred to a 50 liter open head separatoryfunnel and neutralized with two liters of saturated sodium bicarbonatesolution. The reaction mass is then extracted with three 2 literportions of methylene dichloride and the organic layers are washed withone 2 liter portion of sodium chloride solution and then dried overanhydrous sodium sulfate and filtered. The methylene dichloride is thenstripped off and the reaction mass is distilled yielding the followingfractions:

    ______________________________________                                                  Vapor   Liquid           Weight of                                  Fraction  Temp.   Temp.     Pressure                                                                             Fraction                                   Number    (°C.)                                                                          (°C.)                                                                            mm/Hg. (grams)                                    ______________________________________                                        1         32/62   52/64     3.0/3.0                                                                              45.4                                       2         57      60        2.5    109.3                                      3         57      59        2.5    105.4                                      4         58      60        2.5    108.2                                      5         55      68        2.5    98.1                                       6         60      100       2.5    58.0                                       ______________________________________                                    

Fractions 1-6 are bulked. GLC, IR, NMR and mass spectral analyses yieldthe information that fractions 1-6 consist essentially of the compoundhaving the structure: ##STR115##

FIG. 8 is the GLC profile of the crude reaction product prior todistillation (conditions: 2'×1/8" Carbowax column programmed at100°-220° C. at 8° C. per minute).

The peak on the GLC profile indicated by reference numeral "3" is thepeak for the methylene dichloride solvent. The peak indicated byreference numeral "4" is for the product having the structure:##STR116##

The peak indicated by reference numeral "5" is the peak for thecompound, 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone having thestructure: ##STR117##

EXAMPLE VI PERFUME COMPOSITION:

The following mixtures are prepared:

    ______________________________________                                                             Parts by Weight                                          Ingredients            VI(A)   VI(B)                                          ______________________________________                                        Benzyl acetate         50      50                                             Rosewood oil           100     100                                            Cedarwood oil          150     150                                            Linalyl acetate        100     100                                            Alpha-ionone           80      80                                             Ethyl cinnamate        20      20                                             Amyl cinnamic aldehyde 50      50                                             Isoeugenol             50      50                                             Methyl-3-isopropyl-6-methyl-                                                                         50      50                                             resorcylate                                                                   Musk xylene            50      50                                             Styrax resin           100     100                                            Crystalline 4,4A,5,6-tetrahydro-                                                                     30      0                                              7-methyl-2-(3H)-naphthalenone                                                 prepared according to Example                                                 III                                                                           Composition of matter containing                                                                     0       30                                             86% 4,4A,5,6-tetrahydro-7-methyl-                                             2-(3H)-naphthalenone prepared                                                 according to Example IV, fraction 8                                           ______________________________________                                    

The foregoing perfume formulation is an important part of the chypreessence. The coumarin ordinarily in this formulation has been replacedby either crystalline 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenoneor 86% 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone having thestructure: ##STR118## Insofar as the replacement of the coumarin withthe crysalline 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenoneproduced according to Example III is concerned, this chypre essence hasadded to it a coumarin-like, tonka-like, fruity and tobacco-like aromaprofile. Accordingly, the composition of Example VI(A) can be describedas "Chypre with coumarin-like, tonka-like, fruity and tobacco-likeundertones".

The replacement of the coumarin with the composition of matter ofExample IV containing 86%4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone gives rise to a chypreessence having added thereto coumarin-like and sweet rum aroma nuanceswith spicy, hay and tobacco topnotes. Accordingly, the chypre essence ofExample VI(B) can be described as "chypre essence having coumarin-likeand sweet rum undertones and spicy, hay and tobacco-like topnotes".

EXAMPLE VII FOUGERE PERFUME FORMULATION

The following Fougere perfume formulations are prepared:

    ______________________________________                                                             Parts by Weight                                          Ingredients            VII(A)  VII(B)                                         ______________________________________                                        Oakmoss absolute (50% in                                                                             2       2                                              diethyl phthalate)                                                            Bergamot oil           15      15                                             Lavender oil           19      19                                             Citronellol            15      15                                             Patchouli oil          4       4                                              Geranium oil           5       5                                              Gamma methyl ionone    15      15                                             Petitgrain oil         2       2                                              Musk ketone            8       8                                              Heliotropine           2       2                                              Clary sage oil         2       2                                              Amyl salicylate        1       1                                              1,4-benzodioxan-2-one  10      10                                             Crystalline 4,4A,5,6-tetrahydro-                                                                     5       0                                              7-methyl-2-(3H)-naphthalenone                                                 produced according to Example III                                             86% 4,4A,5,6-tetrahydro-7-methyl-                                                                    0       5                                              2-(3H)-naphthalenone produced                                                 according to Example IV, fraction 8                                           ______________________________________                                    

The 1,4-benzodioxan-2-one taken in combination with the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone of our invention givessurprising strength to this Fougere formulation and, in addition, actsas a fixative therefor. Addition of the mixture also creates a naturaland diffusive coumarin-like, tonka-like, fruity and tobacco-like aromain the case of Example VII(A). Accordingly, the fragrance of ExampleVII(A) can be termed as "Fougere with a natural and diffusivecoumarin-like, tonka-like, fruity and tobacco-like undertone". Thecomposition containing 86%4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone prepared according toExample IV (fraction 8) adds to this Fougere formulation a sweet, rumand coumarin-like aroma with spicy, hay and tobacco-like topnotes.Accordingly, the fragrance formulation of Example VII(B) can bedescribed as "Fougere with a coumarin and sweet rum undertone and spicy,hay-like and tobacco-like topnotes".

EXAMPLE VIII PERFUMED LIQUID DETERGENT

Concentrated liquid detergents with aroma nuances as set forth in TableI, infra, are prepared containing 0.10%, 0.15%, and 0.20% of one of thesubstances as set forth in Table I, infra. They are prepared by addingand homogeneously mixing the appropriate quantity of substance set forthin Table I, infra, in the liquid detergent. The detergents all possessaromas as set forth in Table I, infra:

                  TABLE I                                                         ______________________________________                                        Perfume Substance  Aroma Profile                                              ______________________________________                                        Crystalline 4,4A,5,6-tetrahydro-                                                                 A natural and diffusive                                    7-methyl-2-(3H)-naphthalenone                                                                    coumarin-like and tonka-like,                              prepared according to Example                                                                    fruity and tobacco-like                                    III                aroma.                                                     86% 4,4A,5,6-tetrahydro-7-                                                                       A coumarin-like, sweet rum-                                methyl-2-(3H)-naphthalenone pre-                                                                 like aroma with spicy, hay                                 pared according to Example IV,                                                                   and tobacco-like topnotes.                                 distillation fraction 8                                                       Perfume composition of Example                                                                   Chypre with coumarin-like,                                 VI(A)              tonka-like, fruity and                                                        tobacco-like undertones.                                   Perfume composition of Example                                                                   Chypre essence having                                      VI(B)              coumarin-like and sweet                                                       rum undertones and spicy,                                                     hay and tobacco-like                                                          topnotes.                                                  Perfume composition of Example                                                                   Fougere with a natural and                                 VII(A)             diffusive coumarin-like,                                                      tonka-like, fruity and                                                        tobacco-like undertone.                                    Perfume composition of Example                                                                   Fougere with a coumarin                                    VII(B)             and sweet rum undertone                                                       and spicy, hay-like and                                                       tobacco-like topnotes.                                     ______________________________________                                    

EXAMPLE IX PREPARATION OF COLOGNES AND HANDKERCHIEF PERFUMES

Each of the perfumery substances as set forth in Table I of Example VIIIis incorporated individually into colognes at concentrations of 1.5%,2.0%, 2.5%, 3.0%, 3.5% and 4.0% in 80%, 85%, and 90% aqueous ethanol;and into handkerchief perfumes at concentrations of 10%, 15%, 20% and25% (in 80%, 85%, 90% and 95% aqueous ethanol compositions). In each ofthe compositions tested, distinct and definitive aromas as set forth inTable I of Example VIII are imparted to the colognes and to thehandkerchief perfumes.

EXAMPLE X PREPARATION OF A SOAP COMPOSITION

One hundred grams of soap chips (IVORY® manufactured by the Procter &Gamble Company of Cincinnati, Ohio) are mixed with one gram of each ofthe perfumery substances, on an individual basis, of Table I of ExampleVIII. The resulting mixture is melted and maintained at 8 atmospherespressure and 150° C. for a period of 5 hours. The soap is then placed inmolds and the thus formed liquid soap is cooled to room temperature.Each of the soap cakes is then aged for a period of one week under 8atmospheres nitrogen pressure.

Each of the soap cakes manifests a pleasant aroma as set forth in TableI of Example VIII, supra.

EXAMPLE XI PREPARATION OF A SOLID DETERGENT COMPOSITION

A detergent is prepared from the following ingredients according toExample I of Canadian Pat. No. 1,007,948, the specification of which isincorporated by reference herein.

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                         ##STR119##          12                                                       Sodium carbonate    55                                                        Sodium citrate      20                                                        Sodium sulfate, water brighteners                                                                 q.s.                                                      ______________________________________                                    

Each of the detergents is a "phosphate-free" detergent. A total of 100grams of this detergent is admixed with 0.15 grams of each of theperfumery substances of Table I of Example VIII (on an individualbasis). Each of the detergent samples has excellent diffusive aromas asset forth in Table I of Example VIII.

EXAMPLE XII PERFUMED LIQUID DETERGENTS

Concentrated liquid detergents (lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818, issuedon Apr. 6, 1976, the specification of which is incorporated by referenceherein) with aromas as set forth in Table I of Example VIII are preparedcontaining 0.50% of each of the perfumery formulations of Table I ofExample VIII. They are prepared by adding and homogeneously mixing theappropriate quantity of perfume formulation in the liquid detergent. Thedetergents all possess aromas as set forth in Table I of Example VIII.

EXAMPLE XIII FABRIC SOFTENER ARTICLE

Utilizing the procedure of Example 1 of column 15 of U.S. Pat. No.3,632,396 (the disclosure of which is incorporated by reference herein)a non-woven cloth substrate useful as a drier-added fabric softeningarticle of manufacture is prepared wherein the substrate, the substratecoating and the outer coating and the perfuming material are as follows:

1. a water dissolvable paper ("Dissolvo Paper") as the base

2. Adogen 448 (m.p. about 140° F.) as the substrate coating, and

3. an outer coating having the following formulation (m.p. about 150°F.):

    ______________________________________                                         ##STR120##                                                               

    ______________________________________                                    

A fabric softening composition prepared as set forth above having aromacharacteristics as set forth in Table I of Example VIII consists of asubstrate having a weight of about 5 grams per 100 square inches; asubstrate coating having a weight of about 1.85 grams per 100 squareinches of substrate and an outer coating having a weight of about 1.4grams per 100 square inches of substrate, thereby providing a totalaromatized substrate and outer coating weight ratio of about 1:1 byweight of the substrate. The aromas as set forth in Table I of ExampleVIII are imparted in a pleasant manner to the head space in the drier onoperation thereof using the said drier-added fabric softening non-wovenfabric.

EXAMPLE XIV PERFUMED POLYMER

Scented polyethylene pellets having aromas as set forth in Table I ofExample VIII are prepared according to the procedure of Example III ofU.S. Pat. No. 3,505,432 issued on Apr. 7, 1970, the disclosure for whichis incorporated by reference herein. Thus, 75 pounds of polyethylenehaving a melting point of about 220° F. are heated to about 230° F. in acontainer as illustrated in FIGS. 1 and 2 of U.S. Pat. No. 3,505,432.Twenty-five pounds of one of the perfume materials of Table I of ExampleVIII are then quickly added to the liquid polyethylene and the lid inthe apparatus is put in place and the agitating means are actuated. Thetemperature is maintained at about 225° F. and the mixing is continuedfor about 5-15 minutes. The valve is then opened in order to allow flowof the molten polyethylene enriched with the scented material to exitthrough orifices in the apparatus. The liquid falling through theorifices solidifies almost instantaneously upon impact with the movingcooled conveyor part of the apparatus. The solid polyethylene beads orpellets having a pronounced scent as set forth in Table I of ExampleVIII are thus formed. Analysis demonstrates that the pellets containalmost about 25% of the particular perfume substance set forth in TableI of Example VIII so that almost no losses of the scenting substanceoccur. These pellets are called master pellets. Fifty pounds of the saidmaster pellets are then added to 1,000 pounds of unscented polyethylenepowder and the mass is heated to the liquid state. The liquid is moldedinto thin sheets or films. The sheets or films have a pronounced aromaas set forth in Table I of Example VIII. When polypropylene replaces thepolyethylene, a substantially identical result occurs.

EXAMPLE XV VANILLA FLAVOR

The following formulation is prepared:

    ______________________________________                                        Vanillin               10.00  grams                                           Ethyl vanillin         3.00   grams                                           Benzodihydropyrone     3.00   grams                                           Heliotropin            1.00   gram                                            Propenyl guiacol       0.50   gram                                            Gamma nonyl lactone    0.25   gram                                            Gamma undecalactone    0.25   gram                                            Delta dodecalactone    0.25   gram                                            4,4A,5,6-tetrahydro-7- 0.10   gram                                            methyl-2-(3H)-naphthalenone                                                   having the structure:                                                          ##STR121##                                                                   produced according to                                                         Example III                                                                   ______________________________________                                    

The 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone having thestructure: ##STR122## enhances the foregoing vanilla formulation (a)making it more natural-like; (b) imparting a courmarin-like,coconut-like aroma and a coumarin-like, coconut-like, almond-like,macaroon-like taste. The formulation is three times as powerful as theformulation without this compound added thereto. In addition, theformulation is rendered much more outstanding in a standardCreme-de-Kahlua formulation causing the Creme-de-Kahlua formulation tobe more natural-like and preferred by a bench panel of five members,unanimously. The resulting formulation containing the compound havingthe structure: ##STR123## is added to the following liqueur formulation:

    ______________________________________                                        Ingredients       Parts by Weight                                             ______________________________________                                        Clove essential oil                                                                             780                                                         Lemon essential oil                                                                             400                                                         Orange essential oil                                                                            300                                                         Cinnamon essential oil                                                                          250                                                         Mace essential oil                                                                              180                                                         Vanillin formulation (as                                                                        150                                                         set forth above)                                                              Neroli essential oil                                                                            10                                                          Citronellol       2                                                           Rose absolute     1                                                           Food grade ethanol                                                                              927                                                         ______________________________________                                    

The resulting liqueur is added to the following mixture in order toproduce a consumable commercial material:

    ______________________________________                                        Ingredients        Parts by Weight                                            ______________________________________                                        96% food grade ethanol                                                                           301        kg                                              Sugar              40         kg                                              Distilled water    46.8       liters                                          Flavor (as set forth above)                                                                      0.5        kg                                              (0.5% in food grade ethanol)                                                  ______________________________________                                    

The resulting liqueur has an interesting, bitter almond taste and aromawith coconut nuances making it useful as such or as a "Bagne" for asauce used for soaking pound cakes such as "Rum BaBa".

EXAMPLE XVI

The vanilla flavor of Example XV is placed into an ice cream mix at arate of 0.10%. The resulting previously-unflavored ice cream has anexcellent vanilla flavor.

EXAMPLE XVII BASIC WALNUT FLAVOR FORMULATION

The following basic walnut formulation is prepared:

    ______________________________________                                        Ingredients        Parts by Weight                                            ______________________________________                                        Cyclotene          4.0                                                        Vanillin           1.0                                                        Butylisovalerate   2.0                                                        Benzaldehyde       6.0                                                        2,3-diethyl pyrazine                                                                             2.0                                                        (10% in food grade ethanol)                                                   Ethyl-2-methyl valerate                                                                          2.0                                                        Gamma butyrolactone                                                                              20.0                                                       Gamma hexenolactone                                                                              10.0                                                       2,4-decadienal (0.1% in food                                                                     0.5                                                        grade ethyl alcohol)                                                          2,4-heptadienal (0.1% in food                                                                    0.5                                                        grade ethyl alcohol)                                                          Butylidene phthalide                                                                             2.0                                                        Propylene glycol USP                                                                             95.0                                                       ______________________________________                                    

The formulation is divided into two parts. To one of the parts 0.8% byweight of the 86% composition of4,4A,5,6-tetra-7-methyl-2-(3H)-naphthalenone having the structure:##STR124## produced according to Example IV, distillation fraction 8, isadded. To the second part of the basic walnut formulation, nothing elseis added. Both formulations with and without the additional material arecompared at the rate of 100 ppm in water by a bench panel. All membersof the bench panel prefer the walnut flavor with the addition of thecompound prepared according to Example IV having the structure:##STR125## as a result of additional characteristic walnut notes andbitter mouth feel effects being present.

EXAMPLE XVIII A. Powder Flavor Composition

Twenty grams of the flavor composition of Example XVII is emulsified ina solution containing 300 grams gum acacia and 700 grams of water. Theemulsion is spray dried with a Bowen Lab Model Drier utilizing 260c.f.m. of air with an inlet temperature of 500° F. and an outlettemperature of 200° F. and a wheel speed of 50,000 rpm.

B. Sustained Release Flavor

The following mixture is prepared:

    ______________________________________                                        Ingredient              Parts by Weight                                       ______________________________________                                            Liquid walnut flavor composition                                                                          20                                                of Example XVII                                                               Propylene glycol            9                                                 Cab-O-Sil ® M-5 (brand of                                                                             5                                                 silica produced by the Cabot                                                  Corp. of 125 High St., Boston,                                                Mass. 02110                                                                   Physical Properties:                                                          Surface area: 200 m.sup.2 /gm                                                 Nominal particle size: 0.012 microns                                          Density: 2.3 lbs/cu. ft.)                                                 ______________________________________                                    

The Cab-O-Sil® is dispersed in the liquid walnut flavor composition ofExample XVII with vigorous stirring thereby resulting in a viscousliquid. Seventy-one parts by weight of the powder flavor composition ofPart A, supra, is then blended into said viscous liquid with stirring at25° C. for a period of 30 minutes resulting in a dry, free-flowingsustained release flavor powder.

EXAMPLE XIX

Ten parts by weight of 50 Bloom pigskin gelatin is added to ninety partsby weight of water at a temperature of 150° F. The mixture is agitateduntil the gelatin is completely dissolved and the solution is cooled to120° F. Twenty parts by weight of the liquid flavor composition ofExample XVII is added to the solution which is then homogenized to forman emulsion having a particle size typically in the range of 2-5microns. The material is kept at 120° F. under which conditions thegelatin will not gel.

Coacervation is induced by adding slowly and uniformly, forty parts byweight of a 20% aqueous solution of sodium sulphate. During coacervationof gelatin, molecules are deposited uniformly about each oil droplet asa nucleus.

Gelation is effected by pouring the heated coacervate mixture into 1,000parts by weight of a 7% aqueous solution of sodium sulphate at 65° F.The resulting gelled coacervate may be filtered and washed with water attemperatures below the melting point of gelation, to remove the salt.

Hardening of the filter cake, in this example, is effected by washingwith 200 parts by weight of 37% solution of formaldehyde in water. Thecake is then washed to remove the residual formaldehyde.

EXAMPLE XX CHEWING GUM

One hundred parts by weight of chicle are mixed with four parts byweight of the flavor prepared in accordance with Example XVIII, Part B.Three hundred parts of sucrose and one hundred parts of corn syrup areadded. Mixing is effected in a ribbon blender with jacketed side wallsof the type manufactured by the Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips oneinch in width and 0.1 inchs in thickness. The strips are cut intolengths of three inches each. On chewing, the chewing gum has apleasant, long-lasting sweet, fruity, walnut flavor.

EXAMPLE XXI CHEWING GUM

One hundred parts by weight of chicle are mixed with eighteen parts byweight of the flavor prepared in accordance with Example XVIII. Threehundred parts of sucrose and one hundred parts of corn syrup are thenadded. Mixing is effected in a ribbon blender with jacketed side wallsof the type manufactured by the Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips oneinch in width and 0.1 inches in thickness. The strips are cut intolengths of three inches each. On chewing, the chewing gum has apleasant, long-lasting sweet, fruity, walnut flavor.

EXAMPLE XXII TOOTHPASTE FORMULATION

The following separate groups of ingredients are prepared:

    ______________________________________                                        Parts by Weight Ingredients                                                   ______________________________________                                        Group "A"                                                                      30.200             Glycerine                                                  15.325             Distilled water                                            0.100              Sodium benzoate                                            0.125              Saccharin sodium                                           0.400              Stannous fluoride                                         Group "B"                                                                      12.500             Calcium carbonate                                          37.200             Dicalcium phosphate (dihydrate)                           Group "C"                                                                      2.000              Sodium n-lauroyl sarcosinate                                                  (foaming agent)                                           Group "D"                                                                      1.200              Flavor material of Example                                100.000   (total)   XVIII, Part B                                             ______________________________________                                    

Procedure:

1. The ingredients in Group "A" are stirred and heated in a steamjacketed kettle to 160° F.

2. Stirring is continued for an additional three to five minutes to forma homogeneous gel.

3. The powders of Group "B" are added to the gel, while mixing until ahomogeneous paste is formed.

4. With stirring, the flavor of "D" is added and lastly, the sodiumn-lauroyl sarcosinate.

5. The resultant slurry is then blended for one hour.

The completed paste is then transferred to a three roller mill and thenhomogenized, and finally tubed.

The resulting toothpaste, when used in a normal tooth-brushingprocedure, yields a pleasant, sweet, walnut flavor of constant strongintensity throughout said procedure (1-1.5 minutes).

EXAMPLE XXIII CHEWABLE VITAMIN TABLETS

The flavor material produced according to the process of Example XVIII,Part B, is added to a chewable vitamin tablet formulation at a rate of10 gm/kg which chewable vitamin tablet formulation is prepared asfollows:

In a Hobart Mixer, the following materials are blended to homogeneity:

    ______________________________________                                        Ingredients           Gms/1000 Tablets                                        ______________________________________                                        Vitamin C (ascorbic acid as                                                                         70.000                                                  ascorbic acid-sodium ascorbate                                                mixture 1:1)                                                                  Vitamin B.sub.1 (thiamine mononitrate) as                                                           4.000                                                   Rocoat ® thiamine mononitrate 331/3%                                      (Hoffman LaRoche)                                                             Vitamin B.sub.2 (riboflavin) as Rocoat ®                                                        5.000                                                   riboflavin 331/3%                                                             Vitamin B.sub.6 (pyridoxine hydrochloride)                                                          4.000                                                   as Rocoat ® pyridoxine hydrochloride                                      331/3%                                                                        Niacinamide as Rocoat ® niacinamide                                                             33.000                                                  331/3%                                                                        Calcium pantothenate  11.500                                                  Vitamin B.sub.12 (cyanocobalamin) as                                                                3.500                                                   Merck 0.1% in gelatin                                                         Vitamin E (dl-alpha tocopheryl acetate)                                                             6.600                                                   as dry Vitamin E acetate 331/3%                                               Roche                                                                         d-Biotin              0.044                                                   Certified lake color  5.000                                                   Flavor of Example XVIII, Part B                                                                     as indicated above                                      Sweetener sodium saccharin                                                                          1.000                                                   Magnesium stearate lubricant                                                                        10.000                                                  Mannitol q.s. to make 500.000                                                 ______________________________________                                    

Preliminary tablets are prepared by slugging with flat-faced punches andgrinding the slugs to 14 mesh. 13.5 grams dry Vitamin A acetate and 0.6grams Vitamin D are then added as beadlets. The entire blend is thencompressed using concave punches at 0.5 grams each.

Chewing of the resultant tablets yields a pleasant, long-lasting,consistently strong, sweet, walnut flavor for a period of 12 minutes.

EXAMPLE XXIV CHEWING TOBACCO

Onto 100 pounds of tobacco for chewing (85% Wisconsin leaf and 15%Pennsylvania leaf) the following casing is sprayed at a rate of 30%:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                        Corn syrup           60.0                                                     Licorice             10.0                                                     Glycerine            20.0                                                     Fig juice            4.6                                                      Prune juice          5.0                                                      Flavor material of Example XVIII,                                                                  0.4                                                      Part B                                                                        ______________________________________                                    

The resultant product is redired to a moisture content of 20%. Onchewing, this tobacco has an excellent substantially consistent,long-lasting, sweet, green, walnut (20 mnutes) nuance in conjunctionwith the main fruity tobacco note.

EXAMPLE XXV SMOKING TOBACCO FORMULATION

A tobacco mixture is produced by admixing the following ingredients:

    ______________________________________                                        Ingredients     Parts by Weight                                               ______________________________________                                        Bright          40.1                                                          Burley          24.9                                                          Maryland        1.1                                                           Turkish         11.6                                                          Stem (flue cured)                                                                             14.2                                                          Glycerine       2.8                                                           Water           5.3                                                           ______________________________________                                    

Cigarettes are prepared from this tobacco.

The following flavor formulation is prepared:

    ______________________________________                                        Ingredients    Parts by Weight                                                ______________________________________                                        Ethyl butyrate 0.05                                                           Ethyl valerate 0.05                                                           Maltol         2.00                                                           Cocoa extract  26.00                                                          Coffee extract 10.00                                                          Ethyl alcohol  20.00                                                          Water          41.90                                                          ______________________________________                                    

The above-stated tobacco formulation is applied at the rate of 0.1% toall of the cigarettes produced using the above tobacco formulation.One-third of the cigarettes are then treated with 500 or 1,000 ppm of4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone produced according toExample III having the structure: ##STR126##

One-third of the cigarettes are also treated with 500 or 1,000 ppm ofthe 86% mixture of 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenonehaving the structure: ##STR127## prepared according to Example IV,distillation fraction 8.

Control cigarettes not containing4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone produced according toeither of Example III or IV and the experimental cigarettes whichcontain the 4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone producedaccording to Example III and Example IV are then evaluated by pairedcomparison and the results are as follows:

The experimental cigarettes containing the composition preparedaccording to Example III have sweet, lactonic, coconut-like, creamy,coumarin-like, waxy, and heliotropin-like aroma nuances prior tosmoking; and sweet, smoothing rich, coumarin-like aroma and tastenuances on smoking in the main stream and the side stream.

The experimental cigarettes containing the composition of matter ofExample IV, distillation fraction 8, (86% of4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone having the structure:##STR128## have, prior to smoking, a sweet, fruity, juicy, rum-like,sugary, woody and coconut-like aroma and on smoking, a sweet, creamy,coconut-like, rum-like, caramellic-like aroma in the main stream and theside stream.

In general, the products of Examples III and IV enhanced thetobacco-like taste and aroma of blended cigarettes imparting to them, ingeneral, rum-like, sweet and vanilla-like tobacco notes.

EXAMPLE XXVI FLAVORED FOODSTUFF

2.25 ounces of a coconut macaroon mix distributed by Drake BakeriesDivision of Borden, Inc. of Columbus, Ohio 43215 is intimately admixedat the level of 10 ppm with (i) the4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone produced according toExample III or (ii) the 86%4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone composition producedaccording to Example IV (distillation fraction 8).

The coconut macaroon composition contains corn syrup, coconut, sugar andegg whites.

The coconut macaroon composition is then baked at 325° F. at atmosphericpressure for a period of 20 minutes. The resultant coconut macarooncookies have an excellent "natural coconut" coumarin-like note notpresent in the cookies without the compositions of Examples III or IV.

What is claimed is:
 1. A composition of matter comprising4,4A,5,6-tetrahydro-7-methyl-2-(3H)-naphthalenone having the structure:##STR129## and intimately admixed therewith at least one bicycliccompound defined according to the generic structure: ##STR130## whereinZ is benzo or cyclohexano, the proportion of said naphthalenone in saidmixture being from 0.1% up to 99.9% by weight of said mixture.
 2. Aprocess for augmenting or enhancing the aroma or taste of a consumablematerial selected from the group consisting of foodstuffs and perfumecompositions comprising the step of adding to a foodstuff or a perfumecomposition an aroma or taste augmenting or enhancing quantity of amixture defined according to claim 1, said naphthalenone being presentin foodstuffs in an amount of 0.1 parts per million up to about 20 partsper million and said naphthalenone being present in perfume compositionsin an amount of 0.02% to 10%.